Separation of oxygenated organic compounds



Dec. 7, 1954 J. s. CROMEANS' EIAL SEPARATION OF OXYGENATED ORGANIC COMPOUNDS Filed Jan. 4, 1950 INVENTORS. J.S. CROMEANS N.C. CARTER ATTORNEYS United States Patenf O SEPARATIONfOF TOXYGENATED ORGANIC QOMPUUNDS a John S. aCromeans, Dewey; and (Norman. C. .Carter,.- Baritlesvill mflklaagmssignors:- to: Phillips Petroleum Commpanwa: corporation oflDelaware .gp ncafisn, January 4, 1950, Serial aNo. I 136,7 68

" "7 ClaimsZfiCl. 260%450) This invention relates tovtheg'separation of oxygenated organic; compounds. In aone aspect this invention relates in to; a novelprocess- -for;the:recov;ery" ofzoxygenated organic 2 compounds fromwthe. aqueous-phase: of the diluent :firom r as carbon monoxide; hydrogenationvprocess.n In a; more ..,.spe cific; embodiment= .thisrainvention .a-relates to a novel r method of fractionally: distilling? :that :aqueous .phase.

Numerous; problems in the-separation" and recovery of atheoxygenated cornpounds :from': the:;-aqueous% phase of tthe-Eischer-Tropsch productare-well/recognized. :This aqueouszzphase is -comprised; of about 85.- to '90 per. cent -,water, ;the remainder. comprising a-mixtureof' alcohols, ufketones; aldehydeszandwrganicacids: Of these organic :1: oxygenatedcompounds; ethyd alcohol is present in greater amountethan any.-other;single component, its-concentration? oftenbeing in' therrange' 05 40 to '50 volumev per cent;- of theytotalcsoXygenated material. s. The :;numerous components: present; the irelatively small proportionof a ;.1 great many of these components and the many azeotroping mixturesyencountered :thus present: :quite a complex probe-lem int;separation,s-especially when theasepar'ation: must t-e'be economicallypractical to-zbe of anyivalue commercially.

' .cOrdinarilmmthet: processes *zzwherebyz wthese :oxygenated compounds .areseparatedendrecovered utilize afirst step inzwhich ther aqueous-phase is izfractionated to --separate an overhead fraction: in which .:the :aldehydes,tsketonesnand :ilfilQOhOlS' are; concentrated and; anzaqueous' kettle fraction in which the acidic compounds are concentrated. The overhead fraction may their be further processed by 1%,- ordinary -:and extractive 'idistillation, r-solvent extraction and; the like; to recover individual components vthereof. I. The: kettle fraction isalso processed for: recovery of the z: acids" present; *fon. example,- by; neutralization withrv caustic --;and-su;bsequent: evaporation; of :the ywateri and'recovery ofthe men volatile isalts. :The actual: composition: of: :the aqueous .phase' and. ,the'organic;materialrtherein is- :quite mvariable .andw; theyrdependito aizlarge extent rupon lthe reaction conditions: at :whichwther synthesis: reaction is etfectedn In: any-eyent; :the number; of compounds in '.;.:theaqueous phasea'nd'ythe proximity? of boiling -:points of 25 the rindividual:compounds and their-;azeotropes make it tcomparatively dificult toTiobtain -by fractionation alsharp :5: eparationr between the:acid-containingwater; as rkettle product and :the lower boilingoverheadfraction.

1 Itisaan :objecttof 'IhlS1iHV'61'ltl0Il tor-provide axnovel process .forathe, separation of foxygena'tedt organiccompounds.

'1 It is-ranother. objectof this,-inventio'n to provide a novel process for ifractionally distilling :the aqueous-phase -re- 12! sultin'g fromrthe; hydrogenation: of: :c'arbon monoxide.

It is'another object of gthis invention to provide a: novel "r process;for-fractionallywdistilling such. anfiaqueous phase :wto .-obtain=, acid-containing. water as kettle product and lower-boiling oxygenated organic-compounds asoverhead.

'1 It is a further-. objectof .this invention toeifectsuch a I 1 fractional; distillation: to obtain: an improved separation between the kettlerproduct: and-.theoverhead .fraction.

Furtherandadditional objects ofzourv inventionwill be readily; apparent .from-.the detailed. disclosure hereinbelow.

We have found that, in the initial dist-illationiof the aqueou s-phase resulting from/thecatalytic; hydrogenation & Ofncarbon: monoxide, the 'non-ideality of rthe distillation .7. characteristics of t the mixture; makes possible. .an .im-

proved': :method" for; segregating the various components tintoakettle product of uuater;containing;prganioacids,and wanvoverhead iofllower. h il ngscomnonen swh re r the 2,696,495 Patented. Dec. 7, 1954 overall difiiculty of separation is substantiallyidecreased.

We have found that; in ar-continuous:multi-plate. fractionah; distillation. of-- .this aqueousaphase to. separate: an acid-containing: water phase as .a kettle product and ,those 5. co mpou nds :and,.;azeotropes;boiling below .water as. an overhead :product, aa'siderstream. containing oxygenated ,organic compounds.that-wouldgnormally =conta'minate' the kettle product andlor the overheadfraction can be;,withw drawn-from :the fractionaton,-Consequently, the com- 10 pounds thus-removcd ,;Which are relatively high molecular .-.weight'- oxygenated. organic compounds-need not be; re- .-moved from the overhead fraction and the kettle product .i -1n-- -subsequent separate-:operations. The compounds g-thus1removed :are: readily oxidizable to organic, acids; and

as such 'their"removalwandwrecoyery from: the system is facilitated; -Eurthermore, ;the number of different: compounds in the. SidOrSilfifll'II-Zlnd; the low concentration of the-individual compounds .makes'recovery of the individual -compounds difiicult -and uneconomical inmany ,cases.

The; accompanying: drawing is a schematic :diagram of onemethod: of; effecting :our :process. We ahave :inten- :tionally excludedfrom this drawing conventional equipment, such aspumps, -.gauges,-,-compressors, valves, flow I controllers, pressure and temperaturecontrolt-equipment, .1-and they like, but the-inclusion of 1- such equipment is believed-tmbe: readily apparent to one skilled in the: art.

-Referring: now tow-the 1 accompanying; 1 drawing, a l the :waqueous: phase from' the catalyticrhydrogenation of car- ---bon -monoxide:.enters the system; via/line: 10. and passes ,,-hyd;rogenating carbon-monoxide and of separating: the -g-normallyjiquidieffiuent :into ;an; organic-phase and an maqueousphase arewell known in the art and the details of :..those stepslwill'. not tbedncluded. herein. 7 The feed. to fractionaton-jlZ.contains; in addition to Water,- low-boile ging- :alcohols;- acids, .aldehydes and ketones; in varying *proportionsmand,the= feed is introduced to the column 9- at about the midpoint thereof, or-slightly above the mid- ,wp'oint. Theiscolumn is operated in such a, manner-that v the. overhead tractiomcontainspropanol and lower-boil- ;ingcompounds, including a z eotropic water, and-the kettle aproduct contains-organic acids and-water. 1 Towetfect the desired :separationin column 12,- .the overhead tem- !;-..-pe1rat-ure is at least 75 C but below the boilingvpoint 5-: of :water at the operating. pressure. At atmospheric presw -suretthe overhead temperature iswithin -therange of, 75 v, to' 853: C9,: and at a pressure of-30 pounds persquare vinch'gauge-the-overhead-temperature is 105 to 115? C. --Actually,- the use-1ofi.pressureioperation enables a rei-ductiorr in the. size. of the-columnancl in operating costs. --Columny12 is preferably. rated! at atleas-t- 16 theoretical -iplates, and, when rated at.-16 theoretical: plates, the feed is, introduced tothecolumn at aboutr10-.theoretical.plates wabove the-kettle. -.Therrefiux ratio at which columntl2 is.operated-.varies over a.rclatively wide range. Inexperimentalwork we found -a reflux ratiowithinthe range of 3 .5 to .45: to .be satisfactory :and preferable, but reflux e ratioswithin the range of 2.5 to.7.0 orhigher are suitable for our operation. Although .weprefer to introduce-the GOq-feed to: colurnnll at about-:the .midpoint, thefeed may lbe-introduced. totthecolumnwell above the midpoint and belowthe=.top of...the-eolumn., For example, in actual -.experimental :work: employing a e96-wrinch. column,..we ..usualiy.introducedithefeed to the-column-48 inchestabove the.,kettle,..but.we also obtained satisfactory resultswhen the feed-entered 66 inches-above. the kettle. One advangtageis .gained by sintroducingsthe .feed: abovethe mid- ,point, since @the. portion. of the column 1 below the 'feed point acts as a stripping-sectiom. 'By-increasingthe height 7 ofhthis stripping section we decreasedthe concentration markedly in; the kettleproduct of thoseoxygenatedcomtpoundsgthatwe desired to I-iaktfi overhead. The kettle product'from. column 12, containing .organicacids, water, t and: less thanaone. volume .per cent lower-boiling oxygen- 75.,ated organiocompounds; iswithdrawn via line .14. ,The 1 ,overhead traction from column..12, containing lower- ..boiiing. oxygenated organic compounds, is .withdrawn .via 1ine..16. and: condenser .18.'.' .Thateportion of t the over- .head that isnrequired ,for reflux isreturned. to .the column via line 20, and the remaining portionof theoverhead isnrecovered ia line 22. ,The overhead. thus=recovered contains readily separable organic compounds, and it can be treated by any suitable means (not shown), for example, by further fractionation, to recover the individual components or commercially useful mixtures of the components. 7

From a point intermediate the top and bottom of column 12, a side stream is withdrawn via line 24. This draw-off is preferably made above the feed tray to the column but below the tray to which the reflux is returned. However, it is possible to obtain satisfactory results by withdrawing the side stream below the feed tray. The side stream thus withdrawn contains two phases, i. e., an aqueous phase and an organic phase, and the mixture is passed to separator 26 where it stratifies into an upper organic phase and a lower aqueous phase. The organic phase contains butanol and higher boiling alcohols and relatively high molecular weight aldehydes and ketones, i. e., aldehydes and ketones containing at least four carbon atoms per molecule. It is desirable to remove these high molecular weight compounds as described, because they tend to accumulate in column 12, and eventually they contaminate the overhead fraction and kettle product from the column if not removed as described. The solubility characteristics of the components of the side stream determine the composition of the two phases in separator 26, and those components which are miscible in all proportions with water and of relatively high volatility, for example, ethanol, tend to appear in the aqueous phase or to remain in the column as vapor. The organic phase in separator 26 will, of course, contain lower-boiling oxygenated organic compounds, i. e., methanol, ethanol, acetone and acetaldehyde, but these compounds are present in relatively small quantities, particularly when compared with the total amount of these compounds introduced to column 12. In some instances it is desirable to cool the side stream either prior to passage into separator 26 or while in that separator in order to produce the desired distribution of oxygenated compounds between the aqueous and organic phases. The aqueous phase, containing, in addition to water, organic acids and lower-boiling oxygenated compounds, is withdrawn via line 23 and returned to col umn 12, preferably near the point of withdrawal of the side stream. The aqueous phase can be returned to column 12 on the same tray from which the side stream is removed via line 24, and preferably not more than one tray below the point of side stream removal.

The organic phase is removed from separator 26 via line 30. Since this organic phase contains some of the components of the overhead from column 12, it is sometimes desirable to pass the organic phase via line 32 to fractionator 34 where those compounds boiling no higher than propanol are taken overhead via line 36 and admixed with the compounds withdrawn via line 22. The kettle product is withdrawn from column 34 via line 38 and passed via line 40 to oxidation zone 42. In some instances it is uneconomical to separate the low-boiling oxygenated compounds from the organic phase passing via line 30, and, in that event, the organic phase is passed directly to zone 42 via lines 44 and 40. It will be understood that column 34 is considerably smaller than column 12 since the volume of feed to the former is much less than the volume of feed to the latter.

The feed stream to oxidation zone 42 contains readily oxidizable organic compounds, for example, aldehydes and ketones, and in zone 42 these readily oxidizable compounds are oxidized to organic acids. The aldehydes and ketones act as oxidation initiators for the reaction, but, after oxidation has commenced, these compounds are, in turn, oxidized to form organic acids. To effect the oxidation, air or other gas containing substantially no reactive constituent other than oxygen is passed into zone 42 via line 44 and distributor 46. Gaseous effiuent from zone 42 is removed via line 48. The conditions in zone 42 are effective for the conversion of the oxidizable compounds in the feed stream to organic acids. For example, the temperature is within the range of to 150 C. and the pressure is sufficient to maintain the feed in liquid phase, preferably from 1 to 50 atmospheres. The oxidation'reaction can be effected non-catalytically, but it is also within the scope of our process to employ a catalyst for the reaction. Any suitable oxidation catalyst, for example, organic acid salts of manganese, lead, and the like, can be effectively employed in zone 42.

The oxidation product from zone 42 is removed via line 50 and conducted to a separation step (not shown) via line 52. This product contains organic acids andrelatively high-boiling alcohols, for example, butanol and pentanol. In the separation of the oxidation product, the acids are removed by means of a caustic Wash and the remaining oxygenated organic compounds are fractionated into separate cuts comprising essentially single alcohols. Alternatively, the product from zone 42, or a portion thereof, can be withdrawn via lines 50 and 54 and admixed with the kettle product from column 12 passing via line 14. This kettle product contains organic acids similar to those in the product stream from zone 42. In this manner the organic acids from column 12 and zone 42 are recovered in the same recovery steps. It is also within the scope of our process to remove at least some of the water from the kettle product from column 12 prior to recovery of the organic compounds in order to reduce the cost and size of equipment required for the recovery of the organic compounds.

The point at which side stream 24 is withdrawn from column 12 is dependent upon varying factors. Among these variables are the feed rate to the column, the composition of the feed, the column design, the reflux ratio, the point of feed introduction, the desired purity of the overhead fraction and kettle product, and the like. We prefer to Withdraw the side stream above the feed tray, but it is possible to operate the column in such a manner that satisfactory results are obtained by withdrawing the side stream below the feed tray. Such operation tends to increase the concentration of organic acids in the side stream and to reduce the concentration therein of the compounds that we desire to take overhead. Since the oxidation step produces organic acids, it is not necessary to remove the organic acids from the side stream prior to passage to the oxidation step, but a substantial portion of the organic acids is returned to column 12 via line 28.

One of the primary advantages of our process is an increase in the purity of the overhead fraction and/or the kettle product from column 12. If the side stream is not removed from column 12, as described above, the overhead fraction and kettle product contain oxygenated organic compounds whose presence is usually undesirable, and whose presence necessitates additional purification of the overhead fraction and kettle product.

The following example is illustrative of our invention.

Example The aqueous phase recovered from the Fischer-Tropsch condensed efiiuent is continuously fractionated in a column rated at 16 theoretical plates to produce an overhead product comprising principally ethyl alcohol-water azeotrope and lower boiling material, though containing some propanol-water azeotrope. The kettle product comprises water and organic acids. These two fractions are processed by conventional methods for the recovery of pure components or commercially useful mixtures.

A two-phase side stream is withdrawn at a point somewhat above the feed entry, and this side stream is then conducted to a gravity settling tank. The aqueous lower phase is removed and recycled to the column and the upper organic phase is removed to an oxidationtank wherein it is contacted at somewhat elevated temperature with air in order to oxidize the readily-oxidizable components to organic acids. The liquid material recovered is then fractionated to separate those materials boiling in the range of the overhead product (n-propyl alcohol and lighter) from the first fractionation step, these then being combined with the first overhead product for processing to effect a separation of components. The higherboiling portion from this latter fractionation step is then processed by conventional methods to segregate the organic acids, following which the remainder, comprising butanol and higher alcohols, is separated by fractionation. Alternatively, the oxidate or selected fractions thereof may be returned to column 12 if desired.

Numerous modifications and variations within the scope of our invention will be apparent to those skilled in the art from the above disclosure.

We claim:

1. A method for recovering oxygenated organic compounds from the aqueous phase in the normally liquid effluent from the catalytic hydrogenation of carbon monoxide, said aqueous phase consisting of 85 to water and organic compounds comprising alcohols, ketones, aldehydes, and organic acids, which comprises fractionally distilling said aqueous phase to take overhead a fraction containing propanol and lower-boiling organic compounds and to obtain a kettle product containing water and organic acids, withdrawing from said fractional distillation step a side stream containing an aqueous phase including organic acids and lower-boiling oxygenated compounds and an organic phase comprising aldehydes and ketones containing at least 4 carbon atoms per molecule, separating said aqueous phase from said organic phase by stratification in a phase separation zone, and returning said aqueous phase to the fractional distillation step.

2. A method for recovering oxygenated organic compounds from the aqueous phase in the normally liquid efiiuent from the catalytic hydrogenation of carbon monoxide which comprises fractionally distilling said aqueous phase at an overhead temperature of at least 75 C. but below the boiling point of water at the operating pressure so as to recover an overhead fraction containing propanol and lower boiling organic compounds and to obtain a kettle product containing principally water and organic acids, withdrawing from said fractional distillation step a side stream containing an aqueous phase including organic acids and lower-boiling oxygenated compounds and an organic phase comprising aldehydes and ketones containing at least 4 carbon atoms per molecule, separating said aqueous phase from said organic phase by Stratification in a phase separation zone, and returning said aqueous phase to the fractional distillation step. t

3. A method for recovering oxygenated organic 'compounds from the aqueous phase in the normally liquid eiiiuent from the catalytic hydrogenation of carbon monoxide which comprises fractionally distilling said aqueous phase to take overhead and recover a fraction containing propanol and lower-boiling organic compounds and to obtain a kettle product containing water and organic acids, withdrawing from said fractional distillation step a side stream containing an aqueous phase including organic acids and lower-boiling oxygenated compounds and an organic phase comprising aldehydes and ketones containing at least 4 carbon atoms per molecule, separating said aqueous phase from said organic phase by Stratification in a phase separation zone, returning said aqueous phase to the fractional distillation step, oxidizing the aldehydes and ketones in said organic phase to the corresponding acids, and recovering organic acids resulting from said oxidation step and from the kettle product from said fractional distillation step.

4. A method for recovering oxygenated organic compounds from the aqueous phase in the normally liquid effluent from the catalytic hydrogenation of carbon monoxide which comprises introducing said aqueous phase to the midpoint of a fractionating column, fractionally distilling said aqueous phase in said column to take overhead and recover a fraction containing propanol and lowerboiling organic compounds and to obtain a kettle product containing water and organic acids, withdrawing from said column above the point of introduction of said aqueous phase a side stream containing an aqueous phase including organic acids and lower-boiling oxygenated compounds and an organic phase comprising aldehydes and ketones containing at least 4 carbon atoms per molecule, separating said aqueous phase from said organic phase by stratification in a phase separation zone, returning said aqueous phase to the fractional distillation step, oxidizing the aldehydes and ketones in said organic phase to the correspond ing acids, and recovering organic acids resulting from said oxidation step and from the kettle product from said fractional distillation step.

5. The method according to claim 4 wherein the fractional distillation step is effected utilizing a reflux stream at a reflux ratio of 3.5 to 4.5 and wherein the side stream is withdrawn below the point at which the reflux stream enters the column.

6. The method according to claim 4 wherein to effect the oxidation of the organic phase air is contacted with said organic phase at a temperature of 10 to C. and at a pressure sufficient to maintain said organic phase in a liquid phase.

7. A method for recovering oxygenated organic compounds from the aqueous phase in the normally liquid efiiuent from the catalytic hydrogenation of carbon monoxide which comprises introducing said aqueous phase to the midpoint of a fractionating column, fractionally distilling said aqueous phase in said column to take overhead and recover a fraction containing propanol and lower-boiling organic compounds and to obtain a kettle product containing water and organic acids, withdrawing from said column above the point of introduction of said aqueous phase a side stream containing an aqueous phase including organic acids and lower-boiling oxygenated compounds and an organic phase comprising aldehydes and ketones containing at least 4 carbon atoms per molecule, separating said aqueous phase from said organic phase by stratification in a phase separation zone, returning said aqueous phase to the fractional distillation step, fractionating said organic phase so as to take over-head propanol and lower boiling organic compounds contained therein and obtain the heavier aldehydes and ketones as a bottoms fraction, oxidizing the aldehydes and ketones in said bottoms fraction to the corresponding acids, and recovering the resulting organic acids.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,721,959 James July 23, 1929 2,411,809 Rupp et al. Nov. 26, 1946 2,416,377 Chadder Feb. 25, 1947 2,476,788 White July 19, 1949 2,505,752 Burton May 2, 1950 2,558,557 Hess et al. June 26, 1951 2,586,929 Fleming et a1 Feb. 26, 1952 OTHER REFERENCES Robinson et al., Elements of Fractional Distillation, 3d edition (1939), pages 76-80; McGraw-Hill Book Co., Inc., New York. 

1. A METHOD FOR THE RECOVERING OXYGENATED COMPOUNDS FROM THE AQUEOUS PHASE IN THE NORMALLY LIQUID EFFLUENT FROM THE CATALYTIC HYDROGENATION OF CARBON MONOXIDE, SAID AQUEOUS PHASE CONSISTING OF 85 TO 90% WATER AND ORGANIC COMPOUNDS COMPRISING ALCOHOLS, KETONES, ALDEHYDES AND ORGANIC ACIDS, WHICH COMPRISES FRACTIONALLY DISTILLING SAID AQUEOUS PHASE TO TAKE OVERHEAD A FRACTION CONTAINING PROPANOL AND LOWER-BOILING ORGANIC COMPOUNDS AND TO OBTAIN A KETTLE PRODUCT CONTAINING WATER AND ORGANIC ACIDS, WITHDRAWING FROM SAID FRACTIONAL DISTILLATION STEPS OF SIDE STREAM CONTAINING AN AQUEOUS PHASE INCULUDING ORGANIC ACIDS AND LOWER-BOILING OXYGENATED COMPOUNDS AND AN ORGANIC PHASE COMPRISING ALDEHYDES AND KETONES CONTAINING AT LEAST 4 CARBON ATOMS PER MOLECULE, SEPARATING SAID AQUEOUS PHASE FROM SAID ORGANIC PHASE BY STATIFICATION IN A PHASE SEPARATION ZONE, AND RETURNING SAID AQUEOUS PHASE TO THE FRACTIONAL DISTILLATION STEP. 